KR100688642B1 - Composition for production flame retardant insulating material of halogen free type - Google Patents

Abstract

Provided is a composition for preparing a flame-resistant halogen-free insulation material, which has mechanical properties and processability required for insulation coating layers for electric wires, and uses no halogen-containing substance that causes environmental problems. The composition for preparing a flame-resistant halogen-free insulation material comprises: 100 parts by weight of a base resin formed by blending 50-95 wt% of a polyolefin resin and 5-50 wt% of a reactive polyolefin resin into which a polar group is introduced; 50-150 parts by weight of the phosphorus-containing flame retardant; and 30-120 parts by weight of a melamine-based flame retardant. The polar group in the reactive polyolefin resin is any one selected from maleic anhydride and glycidyl methacrylate.

Description

Composition for production flame retardant insulating material of halogen free type

The present invention relates to a composition for producing a flame-retardant non-halogen-based insulating material, and more particularly, by using a blended composite resin as a base resin, by using a phosphorous-based flame retardant and a melamine-based flame retardant at the same time to sufficiently secure the mechanical properties and flame retardancy It relates to an environment-friendly flame-retardant non-halogen-based insulating material manufacturing composition.

In order to be used as an insulating material for electric wires, a flame retardance of a certain degree or more is required, and a method of using a resin composition containing a halogen element is known that has been developed for the purpose of improving the flame retardancy. On the other hand, in the case of an insulating material manufactured using a resin composition containing a halogen element, it is known to suppress the combustion of materials by generating a non-flammable heavy halogen gas during combustion and forming a solidified ash by reacting with an additive. Therefore, in the case of the insulating material manufactured using a halogen-based resin, flame retardancy is basically retained, and various flame retardants are added for the purpose of further improving flame retardancy. The various flame retardants added in this way does not significantly affect the basic physical properties of the base resin, and does not cause an increase in the viscosity of the insulating material, and thus has an advantage of expressing excellent extrusion processability.

As a representative material used as a flame retardant added to the base resin for manufacturing a conventional insulating material, polyvinyl chloride (PVC) may be mentioned, but when the insulating material produced by using the resin composition containing the material is burned, Due to the release of the same toxic gas, it is known to have a harmful effect on the human body and the environment. In connection with this, the development of new materials with relatively low hazards is being progressed along with regulations for environmental protection and interests in the development of environmentally friendly alternative materials.

In the related art, an inorganic metal hydroxide is used as an environmentally friendly flame retardant technology. According to Japanese Patent Application Laid-Open No. 2002-099044, a non-halogen flame-retardant resin composition containing a surface-treated magnesium hydroxide is disclosed. According to Japanese Patent Application Laid-Open No. 2000-245342, a non-halogen-based compound containing a metal hydroxide and a zinc compound is disclosed. A flame retardant resin composition is disclosed. However, in this conventional technique, the amount of the inorganic compound added to improve the flame retardancy is considerable, mechanical properties such as tensile strength and elongation of the insulating material produced therefrom is deteriorated to meet the required product standards. In addition, due to the decrease in workability, reducing the extrusion flux during mass production, productivity is also lowered, and the flexibility of the wire coated with the insulating material produced therefrom greatly reduces the problem of being unable to provide a high-quality product that meets customer requirements. It is pointed out.

Therefore, efforts have been made to solve such problems in the technical field related to the present invention, and the present invention has been devised under such a technical background.

The technical problem to be solved by the present invention based on the above-mentioned conventional problems is to compose a composition containing no halogen element in order to solve environmental problems, and to provide mechanical properties and manufacturing requirements for an insulating material such as an insulating coating layer of an electric wire. The purpose of the present invention is to sufficiently secure the processing and the like, and to provide a composition for producing a flame-retardant non-halogen-based insulating material that can achieve such a technical problem.

In order to achieve the technical problem to be achieved by the present invention, the composition for producing a flame-retardant non-halogen-based insulating material according to the present invention is blended with 50 to 95% by weight of a polyolefin resin resin and 5 to 50% by weight of a reactive polyolefin resin having a polar group introduced therein. 50 to 150 parts by weight of a phosphorus flame retardant based on 100 parts by weight of the base resin; And 30 to 120 parts by weight of a melamine-based flame retardant.

The composition according to the present invention described above is preferably used for producing an insulating coating layer for flame retardant non-halogen-based electric wires.

The present invention will be described in more detail as follows.

The composition for producing a flame-retardant non-halogen-based insulating material according to the present invention comprises a base resin formed by blending a polyolefin resin-based resin and a reactive polyolefin-based resin having a polar group introduced therein, a phosphorous flame-retardant and a melamine-based flame retardant.

The base resin is made by blending 50 to 95% by weight of polyolefin resin with respect to the total weight of the polyolefin resin and 5 to 50% by weight of the reactive polyolefin resin into which the polar group is introduced. Regarding the numerical range of the content of the polyolefin resin of the blended base resin, when the lower limit is reached, the flexibility as the wire insulation is lowered, and when the upper limit is exceeded, the compatibility with the flame retardant is lowered, which is not preferable.

The polyolefin-based resin included in the blended base resin is high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE). Polypropylene (PP), ethylene-1-octene copolymer, ethylene-1-butene copolymer, alphaolefin block copolymer containing 3 to 15 carbon atoms, alphaolefin random copolymer containing 3 to 15 carbon atoms, It is preferable that any one or two or more selected from the group consisting of ethylene vinyl acetate (EVA) copolymers, ethylene ethyl acrylate (EEA) copolymers and ethylene methyl acrylate (EMA) copolymers are mixed.

The polar group used to form the reactive polyolefin-based resin in which the polar group included in the blended base resin is introduced is preferably any one selected from maleic anhydride and glycidyl methacrylate, and the blended base resin The polyolefin-based resin used to form the reactive polyolefin-based resin having a polar group included therein may be any one selected from polyethylene (PE), ethylene vinyl acetate (EVA) copolymer, and ethylene ethyl acrylate (EEA) copolymer. Is preferable.

The polar group used to form the reactive polyolefin-based resin in which the polar group contained in the blended base resin is introduced, is 0.1 to 100 parts by weight of the polyolefin-based resin used to form the reactive polyolefin-based resin in which the polar group is introduced. It is preferable if it is grafted to 5 weight part. Regarding the numerical range for the degree of grafting in the reactive polyolefin-based resin in which the polar group is introduced, when the lower limit is reached, the reaction efficiency is lowered to the extent that the purpose of introducing the polar group is not achieved, which is not preferable, and the upper limit is exceeded. It is not commercially desirable because the actual commercialization is difficult.

The phosphorus flame retardant is preferably included in 50 to 150 parts by weight based on 100 parts by weight of the base resin. Regarding the numerical range of the phosphorus-based flame retardant, it is not preferable that the lower limit value does not exhibit sufficient flame retardant effect, and when the upper limit value is exceeded, the appearance and hygroscopicity of the manufactured product are deteriorated. The phosphorus flame retardant is preferably any one selected from melamine phosphate and melamine polyphosphate.

The melamine flame retardant is preferably included in 30 to 120 parts by weight based on 100 parts by weight of the base resin. With respect to the numerical range for the content of the melamine-based flame retardant, it is not preferable because it does not express a sufficient flame retardant effect if it is lower than the lower limit, it is not preferable because the mechanical properties such as tensile strength and elongation is lowered. The melamine-based flame retardant is preferably melamine cyanurate, and the melamine cyanurate is more preferably any one selected from the group of fatty acid-based and silane-based compounds, if the surface is coated.

In addition, various additives conventionally used to prepare a cable insulation coating layer may be further used in the composition for preparing a flame-retardant non-halogen-based insulation according to the present invention within a range that does not impair the effects of the present invention. Examples of such additives include, but are not limited to, antioxidants, UV inhibitors, thermal stabilizers, lubricants, antiblocking agents, antistatic agents, waxes, coupling agents, pigments, processing aids, carbon black, and the like.

Hereinafter, the present invention will be described with reference to Examples. However, embodiments according to the present invention can be modified in many different forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. Embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.

Example (1-4) and Comparative example (1-4)

As an embodiment according to the present invention, the compositions (divided into Examples 1 to 4) according to Table 1 and Comparative Examples (1 to 4) according to Table 1 were prepared for the purpose of contrast.

division Example (1-4) Comparative example (1-4) One 2 3 4 One 2 3 4 Resin A 80 - 90 - 90 90 90 80 Resin B - 80 - 90 - - - - Resin C 10 10 10 10 10 10 10 10 Resin D 10 10 - - - - - 10 Melamine phosphate 100 - 60 140 100 - 40 170 Melamine polyphosphate - 100 - - - 100 - - Melamine cyanurate 90 90 120 40 25 25 90 90 Lubricant One One One One One One One One Antioxidant One One One One One One One One Crosslinking aid 3 3 3 3 3 3 3 3

In Table 1, the component represented by 'resin A' represents ethylene vinyl acetate copolymer resin containing 33% by weight of vinyl acetate and a melt flow index, and the component represented by 'resin B' contains 33% by weight of vinyl acetate and melted. An ethylene vinyl acetate copolymer resin having a flow index of 0.2, a component represented by 'resin C' represents a low density polyethylene resin into which maleic anhydride is introduced, and a component represented by 'resin D' represents an ethylene vinyl acetate copolymer resin into which maleic anhydride is introduced. Respectively. Low density polyethylene wax was used as the lubricant, pentaerythritol tetrakis as the antioxidant, and trimethyllopropane trimethacrylate was used as the crosslinking aid.

Each of the compositions according to Examples (1 to 4) and Comparative Example (14) having the composition of Table 1 was kneaded in a 3L kneader at 130 ° C. for about 30 minutes to prepare pellets, which were 45 mm in diameter. The electric wire of UL3239 standard was extruded using the extruder whose head temperature is about 165 degreeC. At this time, the thickness of the cable insulation material was 0.5mm, and after irradiation with an irradiation dose of 30 하여 using an electron beam after extrusion, the room temperature properties, flame retardancy and appearance were evaluated and the respective results are shown in Table 2 below.

In the physical properties evaluation at room temperature, the tensile strength and elongation at room temperature were measured according to ASTM D256. The required tensile strength is at least 1.05kgf / mm2, and the elongation is at least 150%. The flame retardancy evaluation was evaluated based on the conformity to the standard of the flame retardant test UL1581-1080 for the vertical flame retardancy (VW-1) evaluation.

division Example (1-4) Comparative example (1-4) One 2 3 4 One 2 3 4 Room temperature Tensile strength (kgf / ㎡) 1.09 1.10 1.12 1.13 1.20 1.30 1.10 0.70 Elongation (%) 182.1 174.5 158.8 161.3 335.1 277.5 180.27 85.3 VW-1 flame retardant test (UL1581-1080) pass fail pass Appearance Evaluation Good Good Bad

As can be seen in Table 2, in both the tensile strength and the elongation rate, which are room temperature characteristics, Examples (1-4) and Comparative Examples (1-3) satisfy the required reference values, but Comparative Example 4 does not. It can be confirmed that it can not be confirmed, the results of the appearance evaluation can be confirmed that the same evaluation. However, according to the flame retardant test results, in the case of Examples (1-4) and Comparative Example 4 passed the test criteria, it can be seen that in the case of Comparative Examples (1-3).

Through these results, in the case of Examples 1 to 4 according to the present invention, since the flame retardancy is sufficiently secured while maintaining the room temperature physical properties, it is confirmed that the composition for producing a highly flame-retardant non-halogen-based insulation material as the present invention is developed. Can be.

Optimal embodiments of the present invention described above have been disclosed. Although specific terms have been used herein, they are used only for the purpose of describing the present invention in detail to those skilled in the art and are not intended to limit the scope of the present invention as defined in the claims or the claims.

According to the present invention, since it does not contain a halogen element in the composition composition used, it can be said that it is more environmentally friendly than conventional halogen-based products in the combustion, it is used in combination by combining a phosphorous flame retardant and melamine flame retardant while using a blended resin By doing so, there is an advantage in that an insulating material product capable of sufficiently exhibiting flame retardancy while satisfying the conditions required for mechanical properties such as tensile strength or elongation can be produced.

Claims (9)

With respect to 100 parts by weight of the base resin, which is blended with 50 to 95% by weight of polyolefin resin and 5 to 50% by weight of reactive polyolefin resin having a polar group introduced therein, 50 to 150 parts by weight of a phosphorus flame retardant; And 30 to 120 parts by weight of a melamine-based flame retardant; composition for producing a flame-retardant non-halogen-based insulating material comprising a. The method of claim 1, The polyolefin-based resin included in the blended base resin is high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE). Polypropylene (PP), ethylene-1-octene copolymer, ethylene-1-butene copolymer, alphaolefin block copolymer containing 3 to 15 carbon atoms, alphaolefin random copolymer containing 3 to 15 carbon atoms, Flame retardant ratio, characterized in that any one or two or more selected from the group consisting of ethylene vinyl acetate (EVA) copolymer, ethylene ethyl acrylate (EEA) copolymer and ethylene methyl acrylate (EMA) copolymer are mixed Composition for producing a halogen-based insulating material. The method of claim 1, The polar group used to form the reactive polyolefin-based resin in which the polar group contained in the blended base resin is introduced is a flame retardant non-halogen-based insulating material, characterized in that any one selected from maleic anhydride and glycidyl methacrylate. Composition for preparation. The method of claim 3, The polyolefin resin used to form a reactive polyolefin resin having a polar group introduced into the blended base resin may be polyethylene (PE), ethylene vinyl acetate (EVA) copolymer, and ethylene ethyl acrylate (EEA) copolymer. Flame retardant non-halogen-based insulating material manufacturing composition, characterized in that any one material selected from. The method of claim 4, wherein The polar group used to form the reactive polyolefin-based resin in which the polar group contained in the blended base resin is introduced, is 0.1 to 100 parts by weight of the polyolefin-based resin used to form the reactive polyolefin-based resin in which the polar group is introduced. A composition for producing a flame-retardant non-halogen-based insulating material, characterized in that the grafted to 5 parts by weight. The method of claim 1, The phosphorus-based flame retardant is a composition for producing a flame-retardant non-halogen-based insulating material, characterized in that any one material selected from melamine phosphate and melamine polyphosphate. The method of claim 1, The melamine flame retardant is a composition for producing a flame-retardant non-halogen-based insulation, characterized in that the melamine cyanurate. The method of claim 7, wherein The melamine cyanurate is a composition for producing a flame-retardant non-halogen-based insulating material, characterized in that the coating is made on the surface of any one selected from the group of fatty acids and silane compounds. The composition according to any one of claims 1 to 8, which is used for producing an insulating coating layer for flame retardant non-halogen-based wires, the composition for producing a flame-retardant non-halogen-based insulating material.